CN103917625A - Spectral luminescence standard for the near infrared region - Google Patents
Spectral luminescence standard for the near infrared region Download PDFInfo
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- CN103917625A CN103917625A CN201280054984.0A CN201280054984A CN103917625A CN 103917625 A CN103917625 A CN 103917625A CN 201280054984 A CN201280054984 A CN 201280054984A CN 103917625 A CN103917625 A CN 103917625A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/74—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth
- C09K11/745—Germanates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/77744—Aluminosilicates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7777—Phosphates
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
- D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
- D21H21/48—Elements suited for physical verification, e.g. by irradiation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
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Abstract
The invention relates to a spectral luminescence standard which comprises Bismuth in a translucent inorganic matrix material and emits light in the near infrared region when exposed to excitation light, wherein Bismuth acts as luminescence emitter in the near infrared region. The invention further relates to a method for producing such a spectral luminescence standard, and to a calibration medium comprising the spectral luminescence standard in or on a carrier material.
Description
The present invention relates to a kind of spectrum emission standards thing (spectral luminescence standard) near infrared region with broadband emission, relate to a kind of method for the manufacture of this emission standards thing, and relate to a kind of spectrum emission standards thing or associated calibrate medium for collimation optical test set or sensor (calibration medium) of presenting.
Value document, such as bank money, check, ID file, credit card, contract etc., be often furnished with the lighting antifalse marker (security feature) for guaranteeing verity.Conventionally in the intended performance process of value document, repeatedly test these anti-counterfeiting marks.
After manufacturing value document or the cheque paper for the manufacture of value document, must test the correct introducing of luminophore or use.This realizes by luminous test set is installed in the appropriate site at security paper material width production line conventionally.Under the help of haulage system, material roll is carried by each production module (section), and so also carry by hard-wired luminous test set, it detects the measurement signal of the material roll in course of conveying.
Value document in circulation, particularly bank money are tested its verity and/or its state in sheet material processing machine, in other situation, also identify for testing its luminous verity.
For this purpose, guiding value document is through detecting the corresponding luminous test set of the luminous signal being sent by this value document.
But, there is such problem: the luminous signal detecting is affected by device dependency, and this even may change in time, what make the luminous measurement that obtains with different devices is relatively infeasible.Therefore, need to pay the clear and definite reference system (so-called emission standards thing) of some target value specification.Under the help of emission standards thing, can calibrate or adjust luminous test set, thereby not in the same time, the measurement of different device can compare each other.
For calibrate for example, arrange along the transport path of material roll (material roll of cheque paper or value document) and for the luminous test set of test material width when the manufactured materials width, conventionally calibrate medium is placed in to the measurement plane of test set, so that by the calibration measurement of this test set testing calibration medium.For this purpose, this calibrate medium can manually be placed in test set in the intercourse of material roll test, thereby calibrate medium replaces material roll to be temporarily arranged in the test surfaces of test set.Calibrate medium is emission standards thing or comprises emission standards thing.Calibrate medium has relative certain target value, and in the time of Measurement and calibration medium, test set detects described certain target value ideally.Under practical situation, usually to determine, actual measured value departs from this target value.So just must readjust test set, thereby the observed value of test set is corresponding to target value that calibrate medium has.As the alternate ways that calibrate medium is manually placed in to test set, can also carry calibrate medium through test set, thus multiple calibration measurement that can testing calibration medium, and can the calibration for test set by the mean value of these observed values.Realize like this calibration more accurately.
At the sheet material working apparatus of the equipment as for value document processing, the verity of wherein for example testing bank money, carries the value document in equipment for example, through sensor, luminescence sensor conventionally.In order to calibrate this sensor, replace value document to carry through sensor suitable calibrate medium, the observed value of this sensor sensing calibrate medium.Calibrate medium is emission standards thing or comprises emission standards thing.Relatively this observed value and the target value relevant to calibrate medium.If the observed value value of departing from objectives must be adjusted sensor so, until when to the remeasuring of calibrate medium its at least close to target value.Then can reuse sensor with test value document.
The requirement of emission standards thing is changed with desired purposes.If emission standards thing is intended to the calibrate medium that acts on the sensor that calibration testing sheet material uses, emission standards thing should provide with the form of sheet calibrate medium so.Also there is different requirements for optical property.For example, substantially, must distinguish the emission standards thing that representative is used for the absorption standard substance of the reference system of measuring luminophore absorption behavior and represents the reference system of the transmitting behavior for measuring luminophore.Standard of wavelength thing (for the reference system of test wavelength accuracy) must have narrow band as much as possible, and spectroscopic standard thing must have spectrum wide as far as possible, level and smooth and Un-structured (unstructured).They should have homogeneity and isotropy and the low temperature dependency of height to meet (apply) for whole standard substances, should be steady in a long-term and light stable, and should be with high as far as possible quantum yield work.
Prior art has provided the emission standards thing of the broadband emission spectrum of visible region, but does not provide any material with broadband and Un-structured transmitting near infrared region.Near infrared region (NIR region) is the wavelength region may of 760～2500nm.
In order to ensure the verity of value document, in other material, use the material of wavelength in transmitting 1000～1500nm region.But, for this region, so far also without any available spectrum emission standards thing, in the time of the excitation light irradiation with suitable wavelength, send broadband and structureless luminous emission standards thing, be not particularly also suitable as so far any spectrum emission standards thing of the emission standards thing of luminescence sensor for being aligned in sheet material working apparatus or paper machine or luminous test set.
Therefore, the object of this invention is to provide the spectrum emission standards thing for 1000～1500nm region, at least in 1000～1500nm region, there is the emission standards thing of luminescence emissions wide, Un-structured.
Another object of the present invention is to describe a kind of method for the manufacture of described emission standards thing.
In addition, the object of this invention is to provide a kind of calibrate medium, it has for the spectrum emission standards thing in 1000～1500nm region and is suitable for calibrated tester or sensor, for example luminescence sensor in sheet material working apparatus or the luminous test set in paper machine.
By thering is the spectrum emission standards thing of feature as claimed in claim 1, by thering is the method for the manufacture emission standards thing of feature as claimed in claim 7, and by thering is the calibrate medium of feature as claimed in claim 10, realize above-mentioned purpose.Embodiments of the present invention are described in the corresponding dependent claims.
Emission standards thing of the present invention has the bismuth as optical transmitting set.Bismuth (III) is known already in the luminosity of visible region.But, the present invention does not use bismuth (III) as NIR optical transmitting set, but use the Bi species near infrared region (NIR region) with broadband emission, the existence of described species is known substantially, and let it be to the greatest extent, and accurate identity (identity) is not completely clear.Technical publications has been discussed Bi
+, Bi
2+, Bi
5+, less positively charged ion or neutral Bi bunch of (for example Bb
2 2+), BiO group and negatively charged ion bismuth species (for example Bi
2 -, Bi
2 2-).Particularly there is the positively charged ion of reduction or the indication of neutral Bi species.For the character that uses Bi species in framework of the present invention, but, their identity definite dispensable.Only need bismuth species to manufacture reliably and repeatablely.Conditions suitable for the manufacture of the Bi species (NIR-Bi) of this NIR-activity is known.The formation special requirement high temperature of the active Bi of NIR-and stablizing in matrix.
In the time using excitation light irradiation, emission standards thing is luminous near infrared region, and the active bismuth of NIR-serves as optical transmitting set.Therefore, luminous near infrared region of emission standards thing is not the Bi (III) that is derived from trivalent, but is derived from the active Bi species of above-mentioned NIR-.The luminous spectral width (FWHM) of NIR-active specy near infrared region is 100nm at least, preferably 200nm at least.Exciting light can be for example in visible spectrum region or near infrared spectrum region, on its energy, be positioned on the near infrared emission of the active Bi species of NIR-.
Suitable body material is for example glass, is specially silicate glass, alumina silicate glass, borosilicate glass, phosphate glass, bismuth germanate glass and oxide glass and chalcogenide glass.In principle, as matrix formation (former), be used to form the parent material of the matrix of the active Bi of NIR-, all inorganic substance and substance mixture that temperature more than approximately 900 ℃ can obtain material by thawing and sintering are suitable, the active Bi of NIR-can stablize in described inorganic substance and substance mixture, and described inorganic substance and substance mixture are abundant printing opacities for exciting radiation and the luminous radiation of the active Bi of NIR-, specifically optically transparent.Realizing optical homogeneity with glass and class glass material is relative the easiest with the transparency, but this is not Compulsory Feature of the present invention.Crystallization with hemicrystalline matrix be also suitable, as long as guarantee that they are stabilized in the bismuth species NIR-Bi of near infrared region broadband emission, and they have the abundant transparency that excites and launch for fluorescent radiation.
The original material (matrix formation) that is suitable for manufacturing body material is for example oxide compound, such as conventionally use when the glass manufacture those.Depend on type of glass, the main component of glass is Si oxide (SiO
2), boron oxide compound (B
2o
3), phosphorous oxides (P
2o
5) and germanium oxide compound (GeO
2).These main components exist with several combinations of the submembers with different basis weights share conventionally." main component " is herein understood as, in its oxide compound % by mole, in total composition, there is the composition of relative lion's share.Various components can be served as main component in some glass, but serve as submember in other glass.For example, boron oxide compound and Si oxide be combined to form borosilicate glass, and aluminum oxide and Si oxide be combined to form alumina silicate glass.
In the present invention, the SiO that silicate glass or alumina silicate glass comprise approximately 50～90 % by mole
2al with 0～40 % by mole
2o
3.The B that borate glass and phosphate glass comprise approximately 30～90 % by mole
2o
3or the P of 30～90 % by mole
2o
5.In addition, can comprise alkalimetal oxide and/or alkaline earth metal oxide and/or the rare-earth oxide as submember.
Basic metal, particularly lithium, increased the luminous intensity of the active Bi of NIR-.Li
2o is preferably contained in body material of the present invention with the quantitative share of 15 % by mole at the most, and Na in some body material mixture
2o and K
2o may reduce luminous intensity, and preferably uses with the quantitative share that is less than separately 5 % by mole.
Basic metal improves the character of glass conventionally, but MgO, CaO, SrO and BaO may weaken luminosity in some cases, be the emittance of the active Bi of NIR-, and therefore used with the quantitative share of body material, be also preferably less than (Mg, Ca, Sr, Ba) O of 5 % by mole.
In the present invention, the preferred submember of body material is rare earth metal, particularly neodymium (Nd), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm) and ytterbium (Yb).These rare earth metals can be used alone or in combination.In matrix, they exist with the form of Tricationic and serve as sensitizer, and they absorb excitation energy and transfer them to the active Bi of NIR-, thereby make exciting of the active Bi of NIR-easier.Therefore, can there is not the spectral shift of the photoluminescent band of the active Bi of NIR-.But, by the rare earth metal doping matrix with suitable,, by bring stack rare earth metal emission band with the luminous spectrum of the active Bi of NIR-, still can expand (extend) emmission spectrum.According to the preferred embodiment of the present invention, with neodymium and the ytterbium matrix that adulterates, thereby by with the emission band stack of Nd and Yb, the shortwave end of emission band even extends further to short wavelength regions.In addition, make Bi-transmitting excite the absorption band that exceeds Nd and Yb by this doping.The luminescence emissions that can realize in shortwave near infrared region by doping Nd and Yb particularly, extends to the wavelength up to about 850nm.Vice versa, according to the present invention another preferred embodiment, by thulium doped and holmium, the long wave end of emission band is by even extending further to Long wavelength region with the emission band stack of Tm and Ho.Therefore, can use and the doping of Tm and Ho extend to up to the wavelength that is greater than 2 μ m with the luminescence emissions realizing in long wave near infrared region.
Rare-earth oxide should comprise the share of 15 % by mole (whole rare-earth oxides) that is body material to the maximum.Under the situation of higher share, concentration quenching may damage luminous.In addition, should avoid adding some rare earth metal, for example Ce.For example Ce of redox active material can hinder the formation of the active Bi of NIR-potentially.
The further preferred submember that improves the luminous intensity of the active Bi of NIR-is TiO
2and ZrO
2, it preferably can comprise respectively the quantitative share of 5 % by mole of body material at the most.The As that can comprise
2o
3, Sb
2o
3, SnO
2and Fe
2o
3preferably be less than respectively the quantitative share of 1 % by mole of body material.These metals stop reduction or the oxidation of the active Bi of NIR-, and promote the formation of the active Bi of NIR-.This is equally applicable to Al
2o
3, it promotes the formation of the active Bi of NIR-especially in silicate glass.Can comprise the aluminum oxide of obvious higher amount, preferably account for the quantitative share of approximately 10～30 % by mole of body material.
In the present invention, use the bismuth of quantitative share, with Bi
2o
3count, account for 0.01～10 % by mole of emission standards thing (bismuth and body material), preferably 0.5～5 % by mole.
Original material for the manufacture of emission standards thing of the present invention is not limited to any form in principle, but preferably uses oxide compound and carbonate or their mixture.This is because being easy to get property and/or the processibility of these materials.
Particularly preferred spectrum emission standards thing of the present invention has the active Bi of NIR-, the Bi that this emission standards thing comprises 1～3 % by mole in glass matrix
2o
3, the SiO of 75～90 % by mole
2, the Al of 10～20 % by mole
2o
3, the Nd of 0.1～0.5 % by mole
2o
3yb with 1～5 % by mole
2o
3.
Above-mentioned chemical formula about the composition of emission standards thing relates to the original material for the manufacture of this emission standards thing.Especially, composition Bi
2o
3as the original material for the manufacture of emission standards thing.Through the manufacturing processed of emission standards thing, by Bi
2o
3form at least partly the active Bi material of NIR-.In the emission standards thing of making, be derived from Bi
2o
3bi be converted at least partly the active Bi material at near-infrared luminous NIR-.
Oxidisability body material, for example oxide glass have above been described.But particularly pointing out body material must be never oxidisability.Certainly, also have other inorganic matrix to be suitable for stablizing NIR-active Bi, specifically chalcogenide glass.
In addition, not only consider that glass is as body material, and consider miocrystalline matrix and crystalloid matrix, for example glass-ceramic and mineral.Be zinc spinel (ZnFe for preferred mineral substrate of the present invention
2o
4), cesium iodide (CsI) and barium pyrophosphate (Ba
2p
2o
7).
Preferably, same, the porous matrix material (ion-exchanger) of crystalloid, for example zeolite and layered silicate, can load have Bi
3+positively charged ion, and then at high temperature activate by forming NIR-Bi-material.So, conventionally destroy crystalline structure, but, there is the product similar with glass melting thing.
In order to manufacture spectrum emission standards thing of the present invention, fully mix original material for example for the oxide compound (where applicable uses in conjunction with carbonate) of glass manufacture or with the mineral of powder morphology, where applicable, add some water to carry out compacting, more fully mix and be dried.If the unbodied inorganic ion exchanger material of for example zeolite and/or layered silicate is as the original material of matrix, do not add so the bismuth of the form such as oxide compound, carbonate that is powder morphology, but first carry out ion-exchange with suitable bismuth salt, to the bismuth positively charged ion of the precursor-filled aequum of base.Then, washing, the dry ion-exchanger through filling, where applicable, further pulverizes, and is similar to the original material that is preferably powder morphology, by its compacting dry.Preferably at the temperature of approximately 40～80 ℃, implement dry approximately 10～15 hours.Then, homogenizing mixture is for example annealed in suitable crucible in corundum crucible or platinum crucible.In order to form the active Bi of NIR-, relatively high original material annealing temperature is necessary.In the time using corundum crucible, need to consider may react with crucible material in some cases, it affects final composition or the aluminium content of product.Essential annealing temperature for example depends on, in the lower work of rare gas element (nitrogen or argon gas) or works in air.In the time heating under atmosphere of inert gases, the temperature of approximately 900 ℃ can be enough to produce the active Bi of NIR-, and while heating in air, requires the temperature of approximately 1300～1800 ℃.Preferably in air, work according to the present invention.
Original material mixture slowly heats (heating rate that per minute is approximately 2～4 ℃) to required target temperature, at this temperature, keeps at least about 3 hours, preferably at least about 4 hours, then slowly cools to room temperature.Rate of cooling is preferably approximately 1～3 ℃ of per minute.
Through annealing process, depend on original material and annealing conditions, obtain glass melting thing or sintered compact.For example zeolite of mineral produces unbodied sintered compact conventionally through high temperature.Be crushed to suitable granularity by the glass through cooling or through cooling sintered compact immediately, for for the calibrate medium with flat material (flat material) form of the present invention, be preferably less than the granularity of 50 μ m.For example in shredder, can implement to pulverize by dry grinding or wet lapping.This pulverizing has the additional advantages of heterogeneous a little product homogenizing in the spatial spectral of making.Conventionally in the emission standards thing with continuous vitreum form, be difficult to realize high space homogeneity.According to the present invention, pulverize emission standards thing preferably to the powder of granularity that is less than 20 μ m.According to the present invention, this small grain size guarantees the mixing property (incorporativity) in particularly preferred spectrum homogeneity and calibrate medium.
Annealing is at high temperature the preferable production process for the active bismuth material of NIR-.But, also may manufacture the Bi component of NIR-activity by irradiating bismuth-containing matrix with gamma-radiation or rich energy electron radiation.This makes the Bi component that at room temperature forms NIR-activity become possibility.Then, high temperature is unnecessary, or may even pass through the generation of the formation again disturbance effect of formed material.
Emission standards thing well known in the prior art be have definition thickness inserts of glass (glass pane) form, with the form of powder, to add the form of the powder additive in lacquer formulations and polymkeric substance, etc.Emission standards thing of the present invention can use with these forms certainly, but wherein its special advantage be emission standards thing of the present invention be extremely suitable among sheet calibrate medium or on.As mentioned above, need sheet calibrate medium to be aligned in luminescence sensor and the luminous test set in paper machine and sheet material working apparatus, particularly need the spectroscopic calibration medium for NIR region.The emission standards thing in inorganic matrix material with the active Bi of NIR-of the present invention is extremely suitable for these objects.
Calibrate medium of the present invention (emission standards thing and carrier) has the flat material of paper carrier or the flat material of plastic carrier or the two.The thickness that the flat material of carrier has, preferably in the scope of approximately 50～300 μ m, is particularly preferably approximately 100 μ m.Emission standards thing of the present invention is introduced in the volume of solid support material, or appears as coating on one or two surface of solid support material.In the time that emission standards thing is introduced in the volume of solid support material, solid support material should be non-absorbent or just weak absorbefacient, must be at least for the luminescence emissions of the active Bi of NIR-and excitation wavelength be enough transmissions so that luminescence emissions may well be detected.The amount of introducing the emission standards thing in solid support material volume preferably falls in the scope of approximately 1～20 % by weight of solid support material, is particularly preferably approximately 5 % by weight of solid support material.If emission standards thing is coated on the surface of solid support material with the form of printing-ink or ink composite or similar liquid composition, so in order to form coating, for dry coating, the emission standards thing of a great deal of is effective, with respect to solid support material, the share of emission standards thing is preferably the amount (being gathered on the surface of solid support material) of approximately 1～10 % by weight.
Calibrate medium of the present invention has the sheet-form that for example defines size (for example size of value document to be tested in sheet material working apparatus).The sheet material of definition size can also be provided as with chip carrier and adhere to, and this may be easy to the operation of calibrate medium.In the situation of sheet material of definition size, emission standards thing can or just extend, be incorporated to the volume of solid support material at the whole area of sheet material on its some region in or as lip-deep coating.In addition, sheet material can comprise the specification about the luminous target value of emission standards thing, and these specifications may for example, become available by the spatial disposition of emission standards thing the form of barcode (with).Certainly, it is available can also making luminous target value specification with different forms, for example on the surface area side of emission standards thing or surface as independent barcode.
Calibrate medium can also have the emission standards thing of also arranging on space, and misorientation is proofreaied and correct in this permission in the time that calibrate medium is located, as what describe in detail in DE10 2,008 048 043 A1, thus with regard to this respect with reference to the disclosure.In addition, calibrate medium of the present invention can be used in further calibration and has corresponding further standard substance, for example standard of wavelength thing, for the standard substance of other optical pickocff or test set or for for example, standard substance for other anti-counterfeiting characteristic (magnetic anti-counterfeit feature or other) calibrating sensors or test set.
The present invention will further be explained on the basis of accompanying drawing below.Ratio and the yardstick that should point out accompanying drawing are not accurately.What represent respectively in addition, is for understanding feature required in this invention.Be apparent that, can exist extra feature or represented feature can also with as in concrete accompanying drawing, represent other be used in combination.Identical Reference numeral refers to respectively identical or corresponding key element.Be depicted as:
Fig. 1 is the emmission spectrum of spectrum emission standards thing of the present invention, and
Fig. 2 to 5 is respectively the schematically showing of different embodiments of calibrate medium of the present invention.
Fig. 1 shows according to the emmission spectrum of the emission standards thing of first embodiment of the invention, and it derives from and consists of (Bi
2o
3)
1.55(Al
2o
3)
14.2(SiO
2)
84.3(Nd
2o
3)
0.159(Yb
2o
3)
3.18glass.Emission standards thing is contained in paper carrier medium.Manufactured as follows spectrum emission standards thing of the present invention: the Bi of the 8.46g that homogenizes in advance in mortar
2o
3, 0.626g Nd
2o
3yb with 14.67g
2o
3, add the SiO of 59.30g
2the Al of (Evonik GmbH, Sipernat50S) and 16.95g
2o
3(SigmaAldrich, 4N nanometer powder) fully mixing all ingredients, then by adding water to carry out compacted powder, again mix, and be dried 12h at 60 ℃.Dried mixture is heated to 1600 ℃ with the speed of 3 ℃ of per minutes in corundum crucible, keeps 4h at 1600 ℃, is then again cooled to room temperature with the speed of 2 ℃ of per minutes.
First pulverize cursorily red-purple glass obtaining thus, then in agate shredder dry grinding 120 minutes to obtain having the glass powder of mean particle size D 99=20 μ m.In order to manufacture calibrate medium of the present invention, with such amount, powder is added to cellulose pulp, make in the time that sheet material is manufactured, in being the final paper of 100 μ m, realizes thickness the relative mass share of the spectrum emission standards thing of 5 % by weight.At the Nd absorption band particularly with for example wavelength 595nm, excite emission standards thing of the present invention, and sheet calibrate medium has the emmission spectrum shown in Fig. 1.Emissive porwer represents with arbitrary unit (a.u.), and transmitting starts from the wavelength below 900nm and terminates at region more than 1600nm clearly.The emissive porwer that can be used for calibration is positioned at the wavelength region may of 900～1600nm.
Use 1mm
2the measurement spot of size has been measured the spectral intensity of 2400 different loci of sheet sample.Determine thus the little standard deviation of departure 7%.Therefore, calibrate medium sheet, pliable and tough has high uniformity.
According to second embodiment, manufacture emission standards thing based on bismuth germanate glass (germanate glass).Suitable content range is specially 1～2 Bi
2o
3, 3～20 Al
2o
3with 80～96 GeO
2(all data in mol%).For example, from composition (Bi
2o
3)
0.9(Al
2o
3)
6(GeO
2)
93.1glass obtain emission standards thing.In order to manufacture emission standards thing, the Bi of 3.89g
2o
3, 5.68g Al
2o
3geO with 90.4g
2homogenizing in mortar.Then add water to carry out compacted powder, again mix, and at 60 ℃ of dry this mixture 12h.The mixture of drying with the gradient-heated to 1600 of 3 ℃ of per minutes ℃ and keep 4h at 1600 ℃, and then is cooled to room temperature with the gradient of 2 ℃ of per minutes in corundum crucible.Resulting materials crush roughly and in agate shredder dry grinding until obtain the glass powder of mean particle size D 99 below 20 μ m.In order to manufacture calibrate medium of the present invention, be, in the time that sheet material is manufactured, in thickness is the final paper of 100 μ m, to have realized the relative mass share of the spectrum emission standards thing of 7 % by weight to the amount of adding this powder in cellulose pulp.In the absorption band of the active Bi material of NIR etc., for example, at 500nm, can excite emission standards thing of the present invention.Broad band transmitting starts from the wavelength below 1000nm, ends at region more than 1600nm.Can be used for the wavelength region may of emissive porwer between 1000～1600nm of calibration.
According to the 3rd embodiment, manufacture emission standards thing based on phosphate glass.Suitable content range is 0.5～2 Bi specifically
2o
3, 10～25 Al
2o
3, 70～90 P
2o
5with 1～3 Yb
2o
3(all data in mol%).For example, by forming (Bi
2o
3)
1,2(Al
2o
3)
20(P
2o
5)
76.8(Yb
2o
3)
2obtain emission standards thing.In order to manufacture this emission standards thing, the Bi of the 2.65g that homogenizes in mortar
2o
3, 9.69g Al
2o
3, 83.9g NH
4h
2pO
4, 3.74g Y
2o
3gac (for annealing atmosphere is set) with 2g.This mixture roasting in corundum crucible (with the gradient increased temperature to 1600 of 3 ℃ of per minutes ℃ and keep 4h at 1600 ℃), and then be cooled to room temperature with 2 ℃ of per minutes.Crush roughly the material of gained, and in agate shredder dry grinding until obtain the glass powder of mean particle size D 99 below 20 μ m.In order to manufacture calibrate medium of the present invention, add this powder to the quantity of cellulose pulp to be, in the time that sheet material is manufactured, the relative mass share that is the spectrum emission standards thing in the final paper of 100 μ m at thickness can reach 6 % by weight.In Yb absorption band etc., for example, excite emission standards thing of the present invention at 980nm.Broad band transmitting starts from the wavelength below 1000nm and ends at region more than 1500nm.Can be used for the wavelength region may of emissive porwer between 1000～1500nm of calibration.
Fig. 2 shows according to the schematic diagram of the embodiment of calibration standard 1 of the present invention.Calibration standard 1 has flaky carrier material 10, and described flaky carrier material 10 is for example made up of paper.Solid support material 10 certainly as select can be formed by plastic material, and can be individual layer or multilayer.Be integrated in the volume of solid support material 10, have the particle 2 of spectrum emission standards thing of the present invention.In the embodiment shown, emission standards composition granule 2 is only arranged in the subregion 5 of solid support material 10, and has the space for the specification of any other standard substance and/or target value in other region.It is evident that, at least, for the wavelength in the excitation wavelength of emission standards thing and the scope of emission wavelength, solid support material 10 must enough penetrate, to guarantee that the suitable of emission standards thing excites and suitable transmitting detectability.
Fig. 3 shows the alternate embodiment of calibrate medium of the present invention.Herein, solid support material 10 has the coating 3 of being made up of emission standards thing of the present invention in the subregion 5 of its first surface 11.In order to prepare coating 3, spectrum emission standards thing of the present invention is for example suspended in mounting medium with fine powder form and is printed on solid support material 10.In the region 6 of the first surface 11 of solid support material 10, be printed with conventional seal ink-stick code 7.This bar code 7 indicates the luminous target value of emission standards thing to be detected in region 5.Coating 3 and bar code 7 can also be placed on the two sides of solid support material 10.
Fig. 4 shows another alternative embodiment of calibrate medium 1 of the present invention.In this embodiment, solid support material 10 has bar code 4 on its whole first surface 11, and its marking by spectrum emission standards thing of the present invention forms.For this purpose, again prepare emission standards thing and be printed to ink or print China ink.Under this situation, bar code 4 provides the specification for the emmission spectrum of calibrated tester and target value to be detected simultaneously.It is evident that, can also on solid support material 10 two-sided, provide the marking 4, to allow, sensor positioned opposite to each other or test set are calibrated simultaneously.This being oppositely arranged is common in sheet material working apparatus, makes it possible to test the two sides of bank money or another kind of value document simultaneously.Certainly, as shown in Figure 4, bar code 4 is not to spread all over respectively all surfaces of solid support material 10, and the subregion of an all right covering surfaces.
Fig. 5 shows another alternative embodiment of calibrate medium 1 of the present invention.In this embodiment, calibrate medium 1 is made up of flaky carrier material 10, and emission standards composition granule 2 is introduced in the volume of this flaky carrier material 10.In embodiment herein, emission standards composition granule 2 is arranged in the whole volume of solid support material 10.At least, for the wavelength in the excitation wavelength of emission standards thing and the scope of emission wavelength, solid support material 10 enough penetrates, to guarantee that the suitable of emission standards thing excites and suitable transmitting detectability.For example can use the solid support material 10 of being made up of paper or plastics, this solid support material 10 is scattering of light, but enough light transmissive.
Calibrate medium 1 has two kinds of other solid support materials 20,30, and for example plastic foil, has the size identical with solid support material 10.Solid support material 20 has first surface 21 and second surface 22, and on second surface 22, is connected for example adhesion with the first surface 21 of solid support material 10.Solid support material 30 has first surface 31 and second surface 32, and on first surface 31, is connected for example adhesion with the second surface 12 of solid support material 10.On the first surface 21 of solid support material 20 and the second surface 32 of solid support material 30, be respectively arranged with the marking 7 of bar code form, this marking is specified the target value of the emission standards thing of the present invention being detected by luminous test set.In addition, solid support material 20,30 is respectively light transmissive, and for example exciting radiation to emission standards thing and emitted radiation are transparent.But the target value bar code marking 7 is not at least light transmissive for the emitted radiation of emission standards thing, but light absorption.Certainly, the tackiness agent that also may use is non-absorbent, or just weak absorbefacient.
If calibrate medium 1 is guided through one or two relative luminescence sensor or luminous test set, sensor or test set detect multiple calibration measurement in the time of scan calibration medium 1 so.But, under the situation of the calibrate medium of Fig. 5, be merely able in bar code gap, detect these observed values, because bar code band even absorbs the light (supposition bar code band allows exciting of emission standards thing) being sent by emission standards thing.Therefore, bar code is guaranteed the modulation (modulation) of the observed value being detected by sensor or test set.This modulation is decoded by sensor or test set, to determine with the calibration required one or more target values relevant to calibrate medium 1.Vice versa, under the situation of the calibrate medium of Fig. 4, is merely able to bring testing calibration observed value in bar code 4.
In the present invention as thering is the flexible sheet of spectrum emission standards thing of the present invention in volume or representing the preferred embodiment of the present invention as the illustrative embodiments of the calibrate medium of the lip-deep marking, because they are particularly suitable for functional for the spectral width belt sensor mode of the paper test machine of specific paper of test.For example sheet shape calibrate medium itself (as paper to be tested) can be introduced in test machine by the conveying roller of test machine.Being distributed in the inner or surperficial broken form of fine powder of sheet shape solid support material, spectrum emission standards thing of the present invention also has especially high homogeneity.Emission standards thing of the present invention or the further advantage with the calibrate medium of emission standards thing of the present invention are the high chemical stability of emission standards thing, stability in storage and photostabilization for a long time.
Claims (15)
1. a spectrum emission standards thing, its light transmissive, particularly in optically transparent inorganic matrix material, there is bismuth, wherein this emission standards thing is luminous near infrared region in the time of excitation light irradiation, and bismuth serves as the optical transmitting set of near infrared region.
2. according to the spectrum emission standards thing of claim 1, it is characterized in that, described inorganic matrix material is glass, particularly silicate glass, alumina silicate glass, borosilicate glass, borate glass, phosphate glass, bismuth germanate glass or chalcogenide glass.
3. according to the spectrum emission standards thing of claim 1 or 2, it is characterized in that, described inorganic matrix material has at least one basic metal and/or at least one alkaline-earth metal for improving luminous intensity.
4. according to the spectrum emission standards thing of any one in claim 1～3, it is characterized in that, described inorganic matrix material is doped with at least one rare earth metal except cerium, and especially, described inorganic matrix material is doped with neodymium and ytterbium.
5. according to the spectrum emission standards thing of any one in claim 1～4, it is characterized in that, described inorganic matrix material has silicon, aluminium, bismuth, neodymium, ytterbium and optional basic metal and/or alkaline-earth metal, on composition, counts the SiO of 75～90 % by mole with oxide compound
2, the Al of 10～20 % by mole
2o
3, the Bi of 1～3 % by mole
2o
3, the Nd of 0.1～0.5 % by mole
2o
3, the Yb of 1～5 % by mole
2o
3.
Bismuth light transmissive, particularly in optically transparent inorganic matrix material as the purposes of emission standards thing, this emission standards thing is luminous near infrared region in the time of excitation light irradiation, wherein bismuth serves as the optical transmitting set of near infrared region, and wherein said emission standards thing has the inorganic matrix material of any one in aforementioned claim especially.
7. one kind for the manufacture of in method light transmissive, that particularly have the spectrum emission standards thing of bismuth in optically transparent inorganic matrix material, wherein said emission standards thing is luminous near infrared region when with excitation light irradiation, and bismuth serves as the optical transmitting set near infrared region, it is characterized in that following steps:
-inorganic bismuth compound and at least one matrix formation are fully mixed to manufacture to the mixture of bismuth-containing, or
With bismuth positively charged ion fill can amorphization inorganic ion exchanger material to manufacture the ionic agent of bismuth-containing;
-under the rare gas element of 900～1800 ℃, or under the air of 1300～1800 ℃, heat the mixture of described bismuth-containing or the ion-exchanger of described bismuth-containing at least 3 hours, preferably at least 4 hours; And
-make the melt of gained or sintered product is cooling and the melt through cooling or sintered product are crushed to the powder of granularity below 50 μ m, the preferably powder below 20 μ m.
8. according to the method for claim 7, it is characterized in that, described bismuth compound and described matrix formation are used as oxide compound and/or carbonate.
9. according to the method for claim 7 or 8, it is characterized in that, in the mixture of described bismuth-containing or the ion-exchanger of described bismuth-containing, add at least one basic metal and/or at least one alkaline-earth metal and/or at least one rare earth metal, it is preferably with the form of oxide compound or carbonate or vitriol or nitrate.
10. a calibrate medium, comprises
-according to the spectrum emission standards thing of any one in claim 1～6, or the spectrum emission standards thing obtaining according to the method for any one in claim 7～9; With
For the solid support material (10) of described emission standards thing.
11. according to the calibrate medium of claim 10, it is characterized in that, described solid support material (10) is sheet, and described spectrum emission standards thing is contained in the volume of described solid support material, or is contained in the subregion of volume of described solid support material.
12. according to the calibrate medium of claim 10, it is characterized in that, described solid support material (10) is sheet, and on one or two surface of described solid support material (10), provides described spectrum emission standards thing as the coating (3) that covers entire area or cover part area.
13. according to the calibrate medium of any one in claim 10～12, it is characterized in that, described calibrate medium has the specification about the luminous target value of spectrum emission standards thing to be detected, described specification specifically obtains by the calibrate medium with barcode, described calibrate medium affects the modulation of the luminous signal that can measure from described emission standards quality testing, and described modulation is corresponding to described luminous target value.
14. according to the calibrate medium of claim 13, it is characterized in that, about the specification of luminous target value to be detected, particularly barcode, by obtaining at spectrum emission standards thing described in the upper spatial disposition of described solid support material (10).
15. according to the calibrate medium of claim 13, it is characterized in that, it at least has another kind of flaky carrier material (20) on a surface of described solid support material (10), it has for the exciting radiation of described emission standards thing and the light transmission region of emitted radiation and not regional transmission of light, wherein about the specification of luminous target value to be detected, particularly barcode, by the light transmission region at described another kind of flaky carrier material (20) and light not the spatial disposition of regional transmission obtain.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102011118057A DE102011118057A1 (en) | 2011-11-09 | 2011-11-09 | Spectral luminescence standard for the near-infrared region |
| DE102011118057.9 | 2011-11-09 | ||
| PCT/EP2012/004625 WO2013068102A1 (en) | 2011-11-09 | 2012-11-07 | Spectral luminescence standard for the near infrared region |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103917625A true CN103917625A (en) | 2014-07-09 |
| CN103917625B CN103917625B (en) | 2016-05-04 |
Family
ID=47148720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280054984.0A Expired - Fee Related CN103917625B (en) | 2011-11-09 | 2012-11-07 | For the spectrum emission standards thing of near infrared region |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US9581540B2 (en) |
| EP (1) | EP2776534B1 (en) |
| CN (1) | CN103917625B (en) |
| AR (1) | AR088656A1 (en) |
| DE (1) | DE102011118057A1 (en) |
| WO (1) | WO2013068102A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110526585A (en) * | 2019-09-26 | 2019-12-03 | 福建师范大学 | A kind of preparation method of anti-forging glass ceramic composite |
| CN114656144A (en) * | 2022-05-07 | 2022-06-24 | 四川和泰光纤有限公司 | Near-infrared luminous tin-bismuth doped aluminosilicate glass optical rod and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102013014401A1 (en) | 2013-08-29 | 2015-03-05 | Giesecke & Devrient Gmbh | Calibration medium for value document sensors |
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| US4598205A (en) * | 1980-05-30 | 1986-07-01 | Gao Gesellschaft Fur Automation Und Organisation Mbh | Security paper with authenticity features in the form of substances luminescing only in the invisible region of the optical spectrum and process for testing the same |
| US20100171076A1 (en) * | 2007-06-13 | 2010-07-08 | Konica Minolta Medical & Graphic, Inc. | Near-infrared light-emitting phosphor nanoparticles, method for manufacturing the same, and biological substance labeling agent employing the same |
| US20100304059A1 (en) * | 2007-09-10 | 2010-12-02 | Saint-Gobain Glass France | Material with photocatalytic properties |
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| FR2420847A2 (en) * | 1978-03-21 | 1979-10-19 | Gravisse Philippe | Wavelength converter for radiation receiver - uses lanthanide(s) dispersed in glass, or lanthanide cpds. dissolved in water, and transmits radiation with increased wavelength |
| EP1439586B1 (en) * | 1996-06-26 | 2014-03-12 | OSRAM Opto Semiconductors GmbH | Light-emitting semiconductor component with luminescence conversion element |
| DE19917887A1 (en) * | 1999-04-20 | 2001-01-18 | Riedel De Haen Gmbh | Inorganic illuminating substance, useful for the production of printing inks and fibers for security documents, is prepared by solid phase synthesis and has specific average particle size |
| DE102004034189B4 (en) | 2004-07-14 | 2019-10-17 | Giesecke+Devrient Currency Technology Gmbh | value document |
| US7608551B2 (en) * | 2005-07-05 | 2009-10-27 | Margaryan Alfred A | Bismuth containing fluorophosphate glass and method for making thereof |
| FR2892196B1 (en) * | 2005-10-18 | 2008-06-20 | Genewave Soc Par Actions Simpl | METHOD FOR MANUFACTURING INTEGRATED DETECTION BIOSENSOR |
| DE102008048043A1 (en) | 2008-09-19 | 2010-03-25 | Giesecke & Devrient Gmbh | Calibrating a sensor for value document processing |
-
2011
- 2011-11-09 DE DE102011118057A patent/DE102011118057A1/en not_active Withdrawn
-
2012
- 2012-11-05 AR ARP120104150A patent/AR088656A1/en active IP Right Grant
- 2012-11-07 US US14/357,301 patent/US9581540B2/en not_active Expired - Fee Related
- 2012-11-07 CN CN201280054984.0A patent/CN103917625B/en not_active Expired - Fee Related
- 2012-11-07 WO PCT/EP2012/004625 patent/WO2013068102A1/en active Application Filing
- 2012-11-07 EP EP12783897.7A patent/EP2776534B1/en active Active
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| US4598205A (en) * | 1980-05-30 | 1986-07-01 | Gao Gesellschaft Fur Automation Und Organisation Mbh | Security paper with authenticity features in the form of substances luminescing only in the invisible region of the optical spectrum and process for testing the same |
| US20100171076A1 (en) * | 2007-06-13 | 2010-07-08 | Konica Minolta Medical & Graphic, Inc. | Near-infrared light-emitting phosphor nanoparticles, method for manufacturing the same, and biological substance labeling agent employing the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110526585A (en) * | 2019-09-26 | 2019-12-03 | 福建师范大学 | A kind of preparation method of anti-forging glass ceramic composite |
| CN110526585B (en) * | 2019-09-26 | 2021-10-19 | 福建师范大学 | Preparation method of anti-counterfeiting glass ceramic composite material |
| CN114656144A (en) * | 2022-05-07 | 2022-06-24 | 四川和泰光纤有限公司 | Near-infrared luminous tin-bismuth doped aluminosilicate glass optical rod and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2776534B1 (en) | 2018-01-10 |
| EP2776534A1 (en) | 2014-09-17 |
| AR088656A1 (en) | 2014-06-25 |
| CN103917625B (en) | 2016-05-04 |
| US9581540B2 (en) | 2017-02-28 |
| DE102011118057A1 (en) | 2013-05-16 |
| WO2013068102A1 (en) | 2013-05-16 |
| US20140284497A1 (en) | 2014-09-25 |
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